Lubricating grease compositions



Patented July 26, 1949 "UNITED;PSTATES PATENT OFFICE LUBRICATING GREASE ooMrosrrioNs, 1 I

Arnold J. Morway, Clark, N. J., assignor to Stand- F ard Oil Development Company, a corporation of Delaware No Drawing. Application November 29,1946,

Serial No. 713,113

4. Claims. (01. 252-30) The present invention relates to lubricating grease compositions and particularly to greases which are designed to resist high temperature and adhere to metallic surfaces in the presence of moisture and under widely varying temperature conditions. i i i In particular thisinvention relates to a grease of the lubricating oil i and carbon black type adapted for use for lubricating large spur gears and other types of roughmachine gears, such as those which are too large to be fully enclosed in gear cases and which for this reason cannot be lubricated with oil. The grease of the present invention is adapted for use in numerous applications Where there is a requirement for moisture-resisting properties and where it is desired that the grease remain on the parts to be lubricated under extreme conditions of hot and cold temperatures. .1.

In the past, large exposed gears have commonly been lubricated with heavy tarry greases such as heavy asphaltic cutbacks. tures such materials are usually satisfactorily adhesive andtheyare water insoluble. Their lubricating properties, however; are not all that might be desired and frequently gears lubricated with such compositions are subject to considerable wear, especially whentheir teeth are not accurately machined. In addition, lubricants of the heavy asphaltic type have. widely different properties at high and low temperatures. Under high temperature conditions such lubricants melt and run off the gear teeth, leaving their surfaces exposed and subject to rapid wear. In cold weather such compounds become excessively hard and brittle and frequently chip and flake away from the gear teeth. In either case the parts to be lubricated are left unprotected. Another disadvantage of the asphaltie type lubricants mentioned above is that they must be heated for application to metal parts in cold weather. Since their specific heat content is relatively low, they frequently congeal rapidly even when heated and thus fail to reach the parts requiring lubrication, and the difficulty of heating and, applying them suitably is in itself a major objection to their use.

Accordingly it is an object of the present inventionto compound a grease which will be free of the above-mentioned objectionable characteristics and which at the same time is relatively inexpensive, easy to applyi and adequately adherent to the parts to be lubricated. q I

Another object of they inyention-is to produce in. .a. novel" and advantageous: manner greases At. normal tempera-.

having the desirable characteristics just mentioned.

Still another object isto-compound a unique gear grease having exceptionally high temperature properties, -a good degree of insolubility in water and good adhesiveness to metals. i

Other objects willbe self-evident as this description proceeds;- I l 1 I. l

In the prior art there have been filed certain applications, of which application Serial No. 570,783, filed December 30, 1944 (now abandoned) is exemplary,?wherein use is made of the properties of certain carbon blacks to impart a greaselike structure to lubricants. These carbonblacks have been referred to]. as structural carbon blacks and are exemplified by the acetylene blacks and the channel blacks of s'mallerparticle sizes. When such carbon blacks are incorporated. in lubricating oil they impart a colloidal structure to the composition which. is quite similar in many respects to the well-known soap grease structure of conventional grease type lubricants. :The structural blacks, so-called; -.may. comprise acetylene blacks havinga pH value of about.8 and having a particle size of the order of '7 acres .per pound of black. The channel blacks, which also may be consideredin this category; may bethose havinga pH valuefror'n 9down to perhaps 4 and having a; particle size which givesthem a surface area of. the orderof 6 ,to 32 acres. per

pound.

Apparently thosejtypes of carbon black which are herein referred to as structural have-either a particulate or reticulate structure, thatis the small particles of carbon, having-average diameters of the orderof 10 to 50 millimicrons, tend to group in clustersor chains. Channel blacks are particulateandtheir grease structure forming properties depend on their high oil absorption due to-small particle size. Acetylene black is reticulate in particle structure and has abnormal oil absorptive-and structure forming properties. The acetylene blacks appear in the form of groups of particles in branched chains giving a reticulate or lacy structure which can be detected by means of the electron microscope and which is particularly suitable for the setting up, DIQS. good grease structure. The carbon .blaclgs of smaller particle size, such as the channel blacks'mentioned above, commonly produce a particulate as distinguished from 'a reticulateor.branchedstructure; In particulate blacks a number of the small individual particles group together i i-clusters which, while not as well adapted toforming a grease structure as the reticulate form of carbon, are nevertheless thoroughly mixed with a structural: carbon black, 7

preferably acetylene blaclgyforms agood lubrie cant of excellent consistency, but is not entirely suitable for use on exposed rough gearing because it lacks certain adhesive qualities. When there are added to such a composition materials which improve its adhesiveness to metal surfaces, the structural carbon blael grease is found: to be hi hl sui able font-he purposes refe red to above- Thus, if a small percentage of a high molecular wei ht polyistgbutylene. i incorporated in the carbon b a y m ro fiqli lnflitfi 'however; p 3- isobutylene otthis. charaeter, when. used in qua tities adequateter mpart a hish des hesiveness to the grease. is unstable to shearing action. which ocsursat the. meshing surfaces of the gears. 'Ehesecompounds soon break down in V viscosity andlosemucheortheiradhesive characteristics- Asphalthasbeen tried for the same purpose. but thisrmateriakcauses the carbon black to lose. its. housing properties .in. the grease. Such a composition becomes fluid and is notsuitable also. improve, theiresistance of the grease to hot water,- even to hot water which is poured over the grease in a-stream. These petroleum resins have high viscosities. I high viscosity indices. Thus, attemperatuires-ofi- 2.10 v their viscosity commonly rangesfrom'99dto8000 S. S. U; These materials per'se are, well-known and are described in some 'detail by Groif and Forrest in 5 Industrial and Engineering, Chemistry, vol. 32,

No.3, pages 294 and29lk (March 1940) When petroleum hydrocarbon resins of the character'just mentioned are added to structural carbon black greasesioomprising mineral oil and acetylene or other structural blacks of the types mentioned above, they render a lubricant quite satisfactory for the hibpication ofexposed rough ears undei various extremesof temperature and. under severe: mistureconditions. They do not adversely afiect the grease-forming characteristics of the carbonblackto any notable extent and they-appear to befunafiected by high rates ofsheari Unlike the polybutene polymers mentioned above,they do not break downunder high shear conditions:suchasgthose that occur in the meshing gear teeth, and they appear to be superior in'some other respects. Furthermore, high concentrations of the resins may be employedwhile more-than 0.2 to 0.3% of high molecular weight polybutene is employed, the rease would become so cohesive that it would'be diflicult to apply "and when; applied couldbe peeledfrom the metal sm faces quite-readily and completely. i l I a I Conventionally -reiined In some of the compositions of the present invention it is considered desirable; though not essential, to employ, in addition to the petroleum resins, small quantities of polybutene in the grease. The character of the adhesiveness imparted to the lubricant by the polybutene constituents is somewhat different from that imparted by the petroleumresins and both properties are desirable in certain respects or for certain purposes.

A typical formula for a satisfactory grease of the "general type mentioned above is as follows:

l Per cent Acetylene black; 12.0 Flowers of sulfur 2.0

Polyisobutenepolymer concentrate (approximately 6 to 7% of high molecular weight polyisobutylene (60,000-80,000 mol. wt) in mineral oil) Petroleum resin from b e- U- at 2.10:

Conventionally refinedlVfid-Qpntinent oil of,

180 S. S. U. viseosityat 219? h e l ne b ack scha eed to. a rease kettle with about one-half of thernineraloil, and agitation is startedf As the massbegins to thicken, the balancegoi the. mineral oil is run into the kettle and the grease. isworked to. a smooth homogeneous mass. before; the. petroleum resin is added. The resin is next worked thoroughly into the composition and finally the polyhutene concentrate and the sulfur are added and thoroughly incorporated intothemixturfl. c I

Agrease. prepared as above is found to have a penetration measure. of 300, no dropping pointor melting point at any reasonable temperature, and it is found to have. fairly highextremeiprea sure properties. Thus, such a grease is found to carry 15 weightsboth in gradual and in shock loading on theAlmen-test machine. 1

In a practical test of a grease. com-pounded as above, the teethof a gearwer ooated athin layer and the gear. then rotated-at 2L0 'RLP. M.

Itwas found that the grease workedjand spread over the surface (if-the gear teeth quite thoroughly and was very adhesive to the metal. he the teeth of the gearwere meshed with another gear, the grease wasiound to become fluidat the point of contact; However, dueto the thir-otropic nature of the grease, it immediately thickened after removal ot-the pi essure, regaining its original consistency. After twentyi-f'ou r hours continuous running, no bare; spots wereno'ted on t'he gear teeth. When the gear; was stopped; no dripping of the grease occurred and nlosparation of the oil from the thic keners was noted.

Comparative tests were conducted; between-several greases of related compositionbyspreading them out on a fiat surface and: playing a stream ofhot water. (about 152 F1) underpressure over thezgreases. The greased surface was; and the test w'as'continued; for aiperiod of ten minutes. following examples give the 'com positions testedi and the'resul ts of the waterwashing tests.

* r nmate! 'Bemea Acetylene black 12.0 Sulfur 2.0

, At' the end of the test period a thin dry film of black grease covered most of the surface, al-

though some parts were found to be completely bare. 1

Example II 1 l Percent Acetylene black 12.0 Sulfur 2.0 Polyisobutene concentrate 1.0

Example III Percent Acetylene black 12.0 Sulfur 2.0 Polyisobutene concentrate 1.0 Petroleum resin 20.0 Mineral oil of 180 S. S. U. at 210 F 65.0

Under the same test conditions a thin film of oily black grease remained on the metal surface after ten minutes with no bare spots appearing. This composition is not fluid and does not run off the surface it is designed to protect.

Example IV A good commercial grade of sodium-soap-compounded grease prepared especially for open gear lubrication was tested under the same conditions and by the end of ten minutes all the grease was completely washed off the surface. A typical composition is as follows:

Percent Sodium soap of hydrogenated fish oil I acids 11.80 Lead oleate 7.15 Asphaltic type mineral oil distillate 10.0 Asphaltic type mineral oil residuum 69.05 Flowers of sulfur 2.00

From the foregoing examples it is evident that carbon black greases without petroleum resins are not highly resistant to the water washing test. Commercial grades of sodium-soap-compounded gear greases are inferior even to the acetylene black greases without petroleum resin. The grease of Example III which included petroleum resins was fully as good in water resisting properties as the heavy asphaltic cutback grease of Example II and had the advantage of retaining a true grease structure, whereas the grease of Example II flowed and dripped off the gears at ordinary temperatures. Examples I and IV were quite unsatisfactory in resistance to water.

While I have given specific examples of ingredients which may be combined to form a highly satisfactory grease composition, it will be understood that any other structural blacks, including the channel blacks of smaller particle size, may be substituted for acetylene black. The percentages used may be varied considerably. Likewise, the particular petroleum resin used may be varied within limits, although I prefer to use those resins having a viscosity of 500 to 10,000 S. S. U. at 210 F. and preferably having a viscosity between 900 and 5000 at the same temperature. The isobutylene polymer may be omitted.

but preferably it is includedin quantities of 0,05 to0.3%. i 7

' Thus, the composition may include from 60 to 90% mineral oil, 2 to 20% carbon black and 1 to 30% petroleum resin together-with a small percentage, preferably 0.1 to of sulfur. A preferred composition will consist of from 65 to 85 of a mineral base lubricating oil, 10 to of a structural carbon black which is preferably acetylene black although not'necessarilyso, 15 toof a petroleum resin having a viscosity between 500 and 10,000 S. S. U. at 210 F., 0.5 to 5% sulfur and from 0.05 to 0.3% of a polymerized hydrocarbon. tackiness agent such as polyisobutylene of high molecular weight -(50,000 to 80,000 mol. wt.)

As indicatedabove, the preferred process is to stir the carbon black into about one-half of. the mineral oil, adding the remainder of mineral oil during the stirring and continuing the stirring to form a substantially homogeneous mass. Thereafter the petroleum resin is added and worked into the mass, and still later the desired percentages of flowers of sulfur and of polybutene (if used) are added, the whole being thoroughly worked to a uniform consistency. It will be apparent that these steps may be varied somewhat but, generally speaking, it is important to obtain the grease structure set-up between the oil and the carbon before the other ingredients are added.

From the foregoing it will be evident that the advantages of structural carbon black greases are obtained in combination with the advantages of the tackycompositions required for use on exposed gearing. While I have described the grease composition of my invention as being particularly adapted for use on exposed gearing, it will be understood that it is useful also for many types of lubrication under varying conditions. It is particularly free from objectionable changes in consistency under extreme temperature changes, remaining fairly firm but sufficiently plastic to afford ease of dispensing and application over a wide range of temperatures, as from 15 F. up to 120 F., or more, and good lubrication from 0 to 300 F. The properties appear to be such that the grease is suitable for uses at higher and lower temperatures than those just mentioned.

Having described my invention, I desire to make it clear that its scope is not to be limited by the foregoing description or otherwise except as required by the following claims:

I claim:

1. A lubricating grease composition comprising 60 to mineral oil, 2 to 20% structural carbon black, selected from the group consisting of acetylene black and channel black of 10 to 50 millimicrons average diameter of abnormally high oil absorptive properties 1 to 30% petroleum resin obtained by propane extraction of deasphaltized petroleum residuums, said resin having a viscosity between 500 and 10,000 S. S. U. at 210 F. and 0.1 to 5% of sulfur.

2. A lubricating grease composition comprising a major proportion of lubricating oil, from 2 to 20% acetylene carbon black, 1 to 30% petroleum resin obtained by propane extraction of deasphaltized petroleum residuums, said resin having a viscosity between 500 and 10,000 S. S. U. at 210 F. and 0.1 to 5% sulfur.

3. A lubricating grease composition comprising approximately 65% mineral lubricating oil, 12% acetylene black, 2% sulfur, 20% petroleum resin obtained by propane extraction of deasphaltized petroleum residuums and 0 to 0.3% of a polymama;

isqhuty ene. .Qf: n 801 0 molecular weigh 4. A lubricating composition comprising; about 65 to 85 of, a mineral base lubricating. Oil; 16350 25 of; acotyleno carbon black 15 M12591; of a petroleum; resin obtaineglby propane extraction of deasphaltized pefiroleum rosiduu-ma havinga viscosityof approximately 50& to 104100 S. 3;. at 210 B 0.51m 5% of sulfun amL fmm 0 to 0.3% Qi ayolymeflzod olefini c hydnooarbon ty 50,099 q 8.0 0Q0-ino1equ1arweight as a tackinewaaont. ARNOLD-I. MQRWAYL REFERENCES, 01min, 1 Tn; fiol l'owing referemcoi axe:- af. recomumtha fire of this patent:

UNITED STATES PAFI'ENTS'Z Name Data 3371390. Belknaprflamwogowmy-w,18835- 1 1 1,;186A67 1. Bierloaa-u; Junefi @919? 245 -58-5 u P um 49. 9 2,323,360 Wallace July 6, 194 3 2,339,898 White Jan. 25, 1944 2,341,134 Adam's Feb. 8, 1944 2,349,058 Swenson May 16, 1944 

